Ethyl diazoacetate → HCID 67074957, compound

HRID 1944094Notes

Reaction equation

HRID 1944094 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:12](=[CH2:31])[O:11][C@H:10]1[C:32]1[CH:37]=[CH:36][C:35]([Cl:38])=[C:34]([CH2:39][C:40]2[CH:45]=[CH:44][C:43]([O:46][CH2:47][CH3:48])=[CH:42][CH:41]=2)[CH:33]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+](=[CH:51][C:52]([O:54][CH2:55][CH3:56])=[O:53])=[N-]>ClCCl.O.C([O-])(=O)C.[Rh+3].C([O-])(=O)C.C([O-])(=O)C>[CH2:55]([O:54][C:52]([CH:51]1[C:12]2([C@@H:13]([O:23][CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[C@H:14]([O:15][CH2:16][C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=3)[C@@H:9]([O:8][CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[C@H:10]([C:32]3[CH:37]=[CH:36][C:35]([Cl:38])=[C:34]([CH2:39][C:40]4[CH:45]=[CH:44][C:43]([O:46][CH2:47][CH3:48])=[CH:42][CH:41]=4)[CH:33]=3)[O:11]2)[CH2:31]1)=[O:53])[CH3:56]

Participants

6

Reactant 2

HCID 12192Ethyl diazoacetateHCID 67075027HCID 67075027, compound

Product 1

HCID 67074957HCID 67074957, compound

Reagents, catalysts & solvents 3

HCID 168478Rhodium acetateCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of (2S,3S,4R,5S)-3,4,5-tris-benzyloxy-2-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-6-methylene-tetrahydro-pyran (See Ex. 1, step III, 100 mg, 0.15 mmole) and rhodium acetate dimmer (0.13 mg, 0.002 mmole) in dry dichloromehane (5 mL), ethyl diazoacetate in dichloromethane (2 mL) was added during 3 hours at room temperature and stirred for 18 hours. The reaction mixture was diluted with water (20 mL) and extracted with DCM (2×30 mL). The crude product was purified by silica gel column chromatography (20% ethyl acetate in hexane) to furnish 50 mg of (5S,6S,7R,8S)-6,7,8-tris-benzyloxy-5-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-4-oxa-spiro[2.5]octane-1-carboxylic acid ethyl ester.

Workup

  1. extractionextracted with DCM (2×30 mL)
  2. customThe crude product was purified by silica gel column chromatography (20% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-8c00cd92401d42f78e485cb40e4a21bd
Source dataset
uspto-grants-2013_03
Patent number
US08394772B2

Reaction notes

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